Surface active agents



United States Patent 3,391,083 SURFACE ACTIVE AGENTS Riyad R. Irani, St. Louis, and Kurt Moedritzer, Webster Groves, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 331,909, Dec. 19, 1963. This application June 29, 1966, Ser. No. 561,360

8 Claims. (Cl. 252-99) This is a continuation-in-part of application Ser. No. 331,909, filed Dec. 19, 1963, now abandoned.

The present invention relates to surface active agents and more particularly to the use of unsymmetrical trialkyl phosphate esters as surface active agents in aqueous systems and to compositions containing the surface active agents.

The water soluble acid esters of orthophosphoric acid are well-known surface active agents. These surface active agents, however, exhibit such undesirable properties as being unstable to heat, readily hydrolyzed, and having poor corrosion characteristics. The neutral tri-alkyl phosphate esters do not exhibit to any appreciable extent the aforementioned undersirable properties, but they are known to be oil soluble and thus their utility in aqueous systems has been, heretofore, unknown. As can be appreciated, therefore, neutral unsymmetrical tri-alkyl phosphate esters which exhibit outstanding properties as surface active agents in aqueous systems and which overcome the objectionable features exhibited by the acid esters of orthophosphoric acid would represent an advancement in this art.

It is, therefore, an object of this invention to provide improved surface active agents for use in aqueous systems.

It is another object of this invention to provide compositions containing the improved surface active agents.

It is still another object of this invention to provide for the use of compositions containing improved surface active agents in aqueous systems.

Other objects will become apparent from a reading of the following detailed description and the claims appended hereto.

It has been found that unsymmetrical tri-alkyl phosphate esters of the following formula RO--i wherein R is an alkyl group containing between about 8 and about carbon atoms and preferably between about 10 and about 14 carbon atoms; and R and R are lower alkyl groups (1-5 carbon atoms) and preferably containing 1 to 2 carbon atoms, unexpectedly exhibit outstanding surface active properties in aqueous systems as will be more fully discussed hereinafter.

Compounds which are suitable for use according to the teachings contained herein include:

(1) diethyl dodecyl phosphate, (C H O) (C H O)PO (2) diisopropyl dodecyl phosphate,

(3) di-n-propyl dodecyl phosphate,

(4) dimethyl octylphosphate, (CH3O)2(C3H170)PO (5) diethyl decylphosphate, (C H O) (C H O)PO (6) dimethyl hexadecyl phosphate,

3,391,083 Patented July 2, 1968 ICC (7) diethyl hexadecylphosphate, (C H O) (C H O)PO (8) di-isopropyl hexadecyl phosphate,

3 e )2( 1s 33 (9) di-n-propyl tetradecyl phosphate,

3 7 )2( 14 29 (10) di-n-butyl hexadecyl phosphate,

t auomcmuamr (l1) di-n-butyl tetradecyl phosphate,

The unsymmetrical tri-alkyl phosphate esters of the present invention can be prepared by many various methods which includes reacting a long chain aliphatic alcohol with phosphorus oxychloride in the presence of a relatively large amount of a dilute inert solvent for the ester, such as hexene or benzene, and an organic base, such as pyridine or triethylamine, containing a tertiary nitrogen atom which reacts with the hydrogen chloride liberated during the reaction to form the hydrochloride of the base. In the same manner, the long chain alkyl haloester formed can then be reacted with lower alkyl alcohols in sufiicient proportions to give the final unsymmetrical tri-alkyl phosphate ester. It is preferred to keep the temperature about 0 C. in order to minimize the possibility of ester-halogen interchange reactions. The following are the reactions in equation form:

Other methods and improvements on the above methods can be used in most instances and include those methods such as found in US. Patent 2,407,279, US. Patent 2,408,- 744, US. Patent 2,410,118, US. Patent 2,426,691 and US. Patent 2,430,569.

The unsymmetrical tri-alkyl phosphate esters of the present invention have been found to be exceptional surface-tension-reducing agents in aqueous systems which can be used for wetting, penetrating, dye-levelling, washing or deterging purposes. This is highly unexpected since the tri-alkyl phosphate esters have been considered as being water-insoluble. However, it has been found that the surface active agents of the present invention are soluble below about .l% by weight in aqueous systems and form relatively stable emulsions in aqueous systems at concentrations up to about 5% by weight. Even though they are only of limited solubility in aqueous systems, they are extremely effective at very low concentrations and, therefore, for most purposes, are soluble in aqueous systems in amounts in which they are effective as surface active agents. Although, in general, these agents can be used as surface active agents in amounts up to about 5% by weight in aqueous systems, that is, in relatively stable aqueous emulsion systems, it is preferred that they be used below about 1% by weight and they can be used in amounts as low as .000l% by weight (1 ppm.) and still be effective. It should be noted that the unsymmetrical tri-alkyl phosphate esters of the present invention are also soluble in aqueous electrolyte solutions to the extent desired to be effective. For example, dimethyl dodecyl phosphate was found to be soluble at about 1% by weight in a 10% sodium sulfate solution, a 10% sulfuric acid solution, and a 10% sodium hydroxide solution.

The following examples are presented to illustrate the invention, with parts by weight being used in the examples unless otherwise indicated.

ill-391,083

4 EXAMPLE I ceramic mixes, floor polishes, detergents including both map and synthetic detergents, and the like.

Because of their ability to reduce the surface tension of aqueous systems at very low concentrations as well as their ability to act as lime soap dispersants, the surface active agents of the present invention are particularly well suited for formulating with soap compositions.

As used herein, the term soap means an alkali metal, ammonium, or amine salt of a fatty acid or mixtures of fatty acids which are capable of being used as washing and cleansing agents in aqueous mediums and any of the water soluble soaps formulated for industrial, household or toilet use may be employed. In addition, the character of the soap constituent may vary widely in its composition Into a reaction vessel are charged about 153.3 grams of POC1 and a mixture of about 186 grams of C H- OH, about 303 grams of N(C H and about 3 liters of hexane. An exothermic reaction takes place and the temperature is maintained by suitable cooling methods at about C. The reaction is complete in about 30 minutes and to this reaction mixture is added about 64 grams of CH OH and again an exothermic reaction takes place with the temperature maintained by suitable cooling 0 methods at about 0 C. After the reaction is completed in about 30 minutes, the precipitate, triethyl amine hydrochloride, is separated from the reaction product and the solvent, hexane, is distilled off to give about 255 grams r r 11 depending on. inter alia, whether the final soap composiof dime hyl dodecyl Phosphate (CH3O)2(C12H25)PO. lion is to be in p p y flake P q EXAMPLE II Mid or other form. Water soluble soaps such as the sodium soaps and other suitable alkali metal, ammonium, or amine In the Same manner as descnbed m t about soaps derived from such fats and oils as tallow, coconut 1533 grams of P003 about 214 m or CMHZQOH'. no oil. cottonseed oil. soy bean oil, corn oil, olive oil, palm about 64 grams of CHSOH were f m l Presenc? or a nil. peanut oil. palm kernal oil, lard, greases, fish oils aboulz 310 grams N(C2H5)3 and 3 mars hexane The and the like as well as their hydrogenated derivatives, reacnon Product dlmethyl tetradecyl phosphate" and mixtures thereof, properly blended to yield the de- (CH O) (C H O)PO sired soap quality may be used in the soap composition lilo of the present invention. Illustrative examples of such after separating the triethyl amine hydrochloride and dismaps Enciude a soap containing about to of tilling off the hexane solvent yields about 195 gram .sodium salts of fatty acids derived from coconut oil and In the following table are given the surface tensions in 1 to of Sodium salts of fatty acids derived from dynes per centimeter of solutions at the indicated concentrations of surface active agents of the instant invention 30 and distilled water at 25 C. as determined by the Du- Nouy princi le using the Fisher Tensiomat. A 1.0% (by weight) solu t ion of each of the agents tested are prepared P and about of potassium Salts of fatty aclds as well as 4 successive lO-fold dilutions of each and alleyrlved from Soy tfean 011 and the f lowed to stand at about for about 4 days. The 35 The amount of the surface active agent necessary to tallow, a soap containing about of sodium salts of fatty acids derived from tallow, a soap containing about 320% of potassium salts of fatty acids derived from cocosurface tension of water is about 72.8 dynes per centiused Wlth Ihe ap may vary, depending upon, inter meter at this temperature. A reduction of the surface tenthe etjld type of soap employed PH condltlons sion of water to 30 dynes in .l% solution is considered the fl in ge ra any amount and especially excellent and if this reduction is maintained practically ilmoums above about 1 Weight Percent based on the Weight unchanged to a dilution as low as that of 003% solution. to of K? in the Compositions exhibit lime p dispersant the material is an extremely active surface-tension-reductt p v however, it is Preferred that amounts from ing agent. titbOut 5 to about 70 weight percent be utilized.

TABLE 1 urfaee Tension in dynes/cm. at 25 0. Compound up, may 91019;, .UOOIZ, (1) Dimethyl dodecylphosphate (CHItO)2(Cl2H250)PO $5.9 $7.0 127.9 39.5 42.0 2) Dimethyltetradecylphosphate (CH:O)1(C14H2 0)PO 45.2 12,4 130.2 l6.7 $7.0

The use of wetting agents in baths for textile treatments 5 The resulting soap composition, that is, the soap and prior to spinning and for similar operations such as dethe surface active agent, is generally effective when used sizing and facilitating penetration of dyes is a well-dein aqueous systems in conventional amounts such as is veloped art. In preparing such baths with the compounds normally used with soap compositions and which is genof the invention, a suitable proportion of the wetting crally above .t)l% concentration. agent is added to give a desired wetting power. From .35 in general. the surface active agent can be used with the comparative results given herein below, the eifectiveany form of the soap, i.e., bar soap, soap flake soap ness of some of the agents at various concentrations for powder. and the like, and can be blended with the use in such baths are indicated and the concentrations of soap prior to the time the final soap composition is formed the surface active agents needed to obtain desired wetting or can be added to the aqueous medium in which the or penetrating powers can be estimated. The values are "50 soap composition is intended to be used prior to or after represented as seconds required to wet a standard cotton the soap composition has been added. The blending operayarn, according to the Draves-Clarkson test as set out tion with soap can be carried out, if desired, in convenin the AATCC 1935-36 Yearbook directions. Values rangtional soap equipment such as a crutcher, or in practicaling from instantaneous in .5 solutions to less than iy any mixing vessel that can be used to formulate soap seconds in .031% solutions are considered excellent. Hi5 (i.e., in which molten soap can be handled), such as 21 TABLE 2 Compound H6391, 031% (1) dimethyl dodecylphosphate tCHsO)z(C1:Hz5O)PO.. .13" to M {MDT (2) Dimethyl tetradecylphosphate (CH O)2(Ci4H2 O)PO LE5 tBO-t- As previously mentioned, the nonionic surface active conventional amalgamator, a conventional refiner, or agents of the present invention can be used in aqueous even a conventional soap mill. After the soap composisystems for wetting properties and surface-tension-reduclion is formed it can generally be handled via convening properties in such diverse fields as dye-processes. texiional techniques and equipment in a manner similar to tile treating processes, ore flotation, plaster, cement and 75 that in which plain or conventional soap is handled; for

example, through the usual plodding, sizing, cooling, stamping and packaging operations. In any event, the surface active agent is intended to be used with the soap at the time of application as a cleansing agent.

Also, the soap compositions in which the surface active agent may be incorporated may contain, if desired, other materials which are commonly used with soaps, such as, synthetic detergents of the anionic and nonionic class, polyphosphate builders, antiredeposition agents (e.g., carboxy methyl cellulose), brightening agents (e.g., fluorescent dyes), bleaching agents and the like as long as the usual considerations of compatability are applied. With respect to the foregoing mentioned synthetic detergents of the anionic and nonionic surface active compound type, these may be any of the conventional detergents which are suitable as cleansing agents. Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and hydrophobic groups in their molecular structure and which ionize in an aqueous medium to give anions containing the hydrophobic group. These compounds are usually the alkali metal salts of organic sulfonates or sulfates, particularly the sodium salts, such as alkyl aryl sulfonates (e.g., sodium dodecylbenzene sulfonate), sulfates of straight chain primary alcohols (e.g., sodium lauryl sulfate) and the like. Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain, usually polyoxyethylene, while the hydrophobic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. For example purposes only, the polyethylene oxide condensates of alkyl phenols (e.g., condensation product for-med from 1 mole phenol and moles ethylene oxide), the condensation products of aliphatic alcohols and ethylene oxide (e.g., condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide) are suitable nonionic surface active compounds in practicing the invention.

The following Table 3 illustrates some of the benefits that can result from utilizing the preferred unsymmetrical trialkyl phosphate esters as lime soap dispersants. Although there are a number of lime soap dispersant tests which can be used, the test which is used herein, i.e., the measurement of the relative stickiness of lime soap scum or curds, has been found to correlate remarkably well with the effectiveness of the lime soap dispersant in actual use. Effective lime soap dispersants decrease or minimize the stickiness of the lime soap curds. In the test, which is conducted at a temperature between and C., 250 parts per million hard water (calculated as CaCO having a Ca:Mg ratio of 2:1 is utilized. Five mls. of a 1 weight percent soap solution (or soap and lime soap dispersant blend) are shaken vigorously in a ml. test tube. Then the resulting foam is immediately stirred slowly into 500 mls. of hard water in -a 600 ml. beaker. After all of the foam is quenched and the solution has stood undisturbed for 2 hours, the amount and particle size of scum, or suspended lime soap curd, are observed and rated in comparison with soap alone and standard soap and lime soap dispersant composition. Soap gives a rating of 10, while the standard soap and lime soap dispersant composition is rated 3 in a test such as that just described.

TABLE 3.-LIME SOAP DISPERSANCY TEST DATA Sample tested Rating (1) Soap control l0 (2) Dimethyl tetradecylphosphate (CH O 2 (C H O)PO (3 Dimethyl dodecyl phosphate (CH O 2 (C H- O PO 1 Lime soap dispersants tested as a 15 weight percent blend of the dispersant with weight percent of soap. The soap is comprised of about 15% of sodium salts of fatty acids derived from coconut oil (primarily lauric acid) and 85% of sodium salts of fatty acids derived from tallow (approximately 40% stearlc acid, 30% oleic acid and 30% palmitic acid).

The surface active agents of the present invention also can be used advantageously as the surfactant or in combination with other surfactants in hard surface cleaning compositions such as scouring powders, dishwashing compositions, products for cleaning floors and walls, and sanitizing compositions.

The dishwashing compositions include, in addition to the surface active agents of the present invention, an alkali material such as the sodium and potassium orthophosphates, hydroxides, sulfates, carbonates and the like; corrosion preventives such as the sodium and potassium orthosilicates and metasilicates; sequesterants such as sodium and potassium polyphosphates (sodium tripolyphos phate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate), -amino polycarboxylates, (tetrasodium ethylenediaminetetraacetic acid, trisodium nit-rilotriacetate and tripotassium nitrilotriacetate), -gluconates (sodium gluconate and potassium gluconate, and the -polyphosphonates (penta sodium aminotrimethylphosphonate, tetrasodium methyldiphosphonate, tetrasodium l-hydroxy, ethylidenediphosphonate and tripotassium l-hydroxy, ethylidene diphosphonate) and the like; and sanitizers such as the hvpochlorites including the alkali metal hypochlorites such as sodium hypochlorite and lithium hypochlorite and the alkaline earth metal hypochlorites such as calcium hypochlorites and the chlorinated trisodium phosphates as described and disclosed in United States Patent 1,555,474 and 1,965,304 as well as organic chlorine-developing compounds which include the alkyl hypochlorites and especially the lower alkyl chlorites such as ethyl hypochlorites, propyl hypochlorites, n-butyl hypochlorites, and tert-butyl-hypochlorite; the nchlorinated heterocyclic compounds and especially the 5- and 6-membered n-chlorinated heterocyclic compounds such as hydantoin, n-chlorosuccinimide, and the triazines, such as the cyanuric acids and salts which include trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, and potassium dichloroisocyanurate, as well as melamine, ammeline and ammelide; and the n-chloroaromatic and substituted aromatic such as sodium benzene sulfochloroamide, and sodium p-toluene sulfonchloroamide.

The term active or available chlorine is commonly used in the hypochlorite bleaching and sterilizing art to refer to atomic or nascent chlorine. Such chlorine differs from normally occurring chlorine in that the latter occurs in molecular form and each molecule contains two atoms of chlorine. When employed for bleaching or sterilizing purposes the active or available chlorine has twice the oxidizing or bleaching activity of molecular chlorine, based on the weight (molecular) of the normally occurring molecular chlorine. Thus, the terms active or available chlorine are generally expressed as twice the amount in terms of percent of the chlorine present in a molecule of material.

Due to the many and varied chlorine-releasing agents which vary in molecular weight and available chlorine over a wide range and the fact that the amounts of the chlorine-releasing agent used in many applications are based on the available chlorine content, the amounts suitable for use herein unless otherwise indicated will be based on percent available chlorine per total weight of the particular composition. By knowing the molecular weight of the particular chlorine-releasing agent, its available chlorine, and the available chlorine desired expressed in percent available chlorine per total weight of the particular composition, the necessary amounts on a weight basis can readily be determined.

The dishwashing composition can be prepared by, in general, admixing the additives, i.e., the surface active agent, alkali material, corrosion preventive, sequestering agent and sanitizer, in any order, although it may at times be advantageous to first absorb the surface active agent on a solid additive such as the alkali metal and/ or lllcll91,083

iv the sequestering agent and then formulate by mixing with the other additives.

The following additives within the ranges specified give an effective dishwashing formulation Chlorine-releasing agent:

Percent available chlorine per total weight of The following composition (parts by weight) is especially adapted for use as a machine dishwashing composition when used in amounts to give about 15 to 35 ppm. available chlorine in the water.

The sanitizing compositions which are especially useful for washing articles, such as bottles and glassware are comprised of, in addition to the surface active agents of the present invention, alkali cleansers and a sequestering agent.

The alkali cleansers which may be used to practice the invention are inorganic compounds, such as the watersoluble compounds of the alkali metal and ammonium hydroxides (e.g., NaOH and KOH) and alkali metal and ammonium carbonates (e.g., Na CO3), including mixtures thereof, which are suitable for washing articles in strongly alkaline solutions. Because of its availability and relative inexpensiveness sodium hydroxide lNaOH) is usually the major ingredient of most alkali cleansers and is, therefore, preferred.

The sequestering agents which can be used to practice the invention are any water-soluble sequestering agents which are effective in sequestering calcium and magnesium under relatively high pH and temperature conditions and include such sequestering agents as the sodium and potassium -polyphosphates [sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate), -amino polycarboxylates, {tetrasodium ethylenediaminetetraacetic acid, trisodium nitrilotriacetate and tripotassium nitrilotriacetate,) -gluconates lsOdium gluconate and potassium gluconate) and the -polyphosphonates (penta sodium aminotrimethylphosphonate, tetrasodium methyldiphosphonate, tetrasodium l-hydroxy, ethylidenediphosphonate and tn'potassium l-hydroxy, ethylidene diphosphonate) and the like.

The sanitizing compositions can be prepared by, in general, admixing the additives, i.e., the surface active agents, alkali cleansers, and sequestering agents, in any order. although it may at times be advantageous to first absorb the surface active agent on a solid additive such as the alkali cleanser and/or sequestering agent and then formulating the sanitizing composition by mixing with the other additives.

Because the sanitizing compositions are primarily directed to compositions for washing articles, such as bottles and glassware, the washing solution should preferably exhibit effective germicidal action as well as cleansing action without adversely affecting the articles. The effects of soaking time, alkaline concentration, and temperature are interrelated in the sense that increased temperatures and/ or concentrations diminish the washing period required to attain a given standard of cleansing and germicidal performance. In general, the temperature ranges are usually taken to be about 120-165 F2, and the concentration of the alkali cleansers in the alkaline washing solution are ill 8 usually taken to be about .l-5% by weight; although as gh as 30% alkali detergent can be employed under cerin conditions.

Ilbe following additives within the ranges specified on a percent by weight basis give an effective bottle washing composition.

Alkali cleanser 5-90 equestering agent 1-50 surface active agent .5-30

The following composition on a percent by weight basis is especially adapted for use in aqueous solutions at about l by weight concentration for washing bottles.

llodium hydroxide 68 Sodium gluconate 30 IlDimethyl tetradecyl phosphate 2 What is claimed is:

ill. A dishwashing composition consisting essentially of a chlorine-releasing agent in an amount between about l$% to 2.0% available chlorine per total weight of said composition, a material selected from the group consisting ct sodium and potassium orthophosphates, hydroxides, carbonates and sulfates in an amount of from about 40% to about 60% by weight of said composition, a silicate corrosion preventive selected from the group consisting of sodium and potassium orthosilicates and metasilicates in amount of from about to about by weight of said composition, a sequestering agent selected from the group consisting of sodium and potassium tripolyphosphates, pyrophosphates, amino polycarboxylates, gluconates, amino tri(methylenephosphonates), methylenediphos-phonates, and l-hydroxy, ethylidene diphosphonates, in an amount of from about 1% to about by weight bf said composition and, as a surface active agent, an unsymmetrical tri-alkyl phosphate ester in an amount of t'rom about 1 to about 10% by weight of said composition and of the following formula cc/herein R is an alkyl group between about 8 and about 20 carbon atoms and R and R are lower alkyl groups containing from l to 5 carbon atoms.

it. A composition according to claim 1, wherein said ll'ri-alkyl phosphate ester is of the following formula wherein R is an alkyl group containing between about 10 and about 14 carbon atoms and R and R are lower alkyl groups containing 1 to 2 carbon atoms.

A dishwashing composition according to claim 2, wherein said phosphate ester is dimethyl dodecyl phosphate.

al. A dishwashing composition according to claim 2, wherein said phosphate ester is dimethyl tetradecyl phosphate.

b. An alkaline washing composition consisting essentially of an alkali cleanser selected from the group consisting of alkali metal and ammonium hydroxides, carbonates and mixtures thereof in an amount from about to about 90% by weight of said composition, a sequestering agent selected from the group consisting of sodium and potassium tripolyphosphates, pyrophosphates, amino polycarboxylates, gluconates, amino tri(rnethylenephosphonates methylenediphosphonates and l-hydroxy, cthylidene diphosphonates, in an amount of from about l.% to about by weight of said composition and, as ct surface active agent, an unsymmetrical tri-alkyl phosphate ester in an amount from about 0.5 to about 30% by weight of said composition and of the following formula 11 RO-P wherein R is an alkyl group containing between about 8 and about 20 carbon atoms and R and R are lower alkyl groups containing from 1 to 5 canbon atoms.

6. A composition according to claim 5, wherein said tri-alkyl phosphate ester is of the following formula wherein R is an alkyl group containing between about 10 and about 14 carbon atoms and R and R are lower alkyl groups containing from 1 to 2 carbon atoms.

7. An alkaline washing composition according to claim 10 6, wherein said phosphate ester is dimethyl dodecyl phosphate.

8. An alkaline washing composition according to claim 6, wherein said phosphate ester is dimethyl tetradecyl phosphate.

References Cited UNITED STATES PATENTS LEON D. ROSDOL, Primary Examiner. MAYER WEINBLATT, Assistant Examiner. 

1. A DISHWASHING COMPOSITION CONSISTING ESSENTIALLY OF A CHLORINE-RELEASING AGENT IN AN AMOUNT BETWEEN ABOUT 0.5% TO 2.0% AVAILABLE CHLORINE PER TOTAL WEIGHT OF SAID COMPOSITION, A MATRIAL SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM ORTHOPHOSPHATES, HYDROXIDES, CARBONATE AND SULFATES IN AN AMOUNT OF FROM ABOUT 40% TO ABOUT 60% BY WEIGHT OF SAID COMPOSITION, A SILICATE CORROSION PREVENTIVE SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM ORTHOSILICATES AND METASILICATES IN AN AMOUNT OF FROM ABOUT 10% TO ABOUT 30% BY WEIGHT OF SAID COMPOSITION, A SEQUESTERING AGENT SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM TRIPOLYPHOSPHATES, PYROPHOSPHATES, AMINO POLYCARBOXYLATES, GLUCONATES, AMINO TRI(METHYLENEPHOSPHONATES), METHYLENEDIPHOSPHONATES, AND 1-HYDROXY, ETHYLIDENE DIPHOSPHONATES, IN AN AMOUNT OF FROM ABOUT 1% TO ABOUT 40% BY WEIGHT OF SAID COMPOSITION AND, AS A SURFACE ACTIVE AGENT, AN UNSYMMETRICAL TRI-ALKYL PHOSPHATE ESTER IN AN AMOUNT OF FROM ABOUT 1 TO ABOUT 10% BY WEIGHT OF SAID COMPOSITION AND OF THE FOLLOWING FORMULA 